Process for the polymerization of ethylene in the presence of a ziegler-type catalyst and as a catalytic modifter a polydentate compound



United States Patent Pennsylvania No Drawing. Filed Aug. 5, 1960, Ser.No. 47,620 22 Claims. (Cl. 260-943) This application is acontinuation-in-part of Serial No. 858,590, filed December ll), 1959,and now abandoned.

This invention relates to synthetic polymers. More particularly, thisinvention is concerned with novel catalyst compositions and processes ofproducing resinous polyethylene using the catalyst compositions.

It is known that Ziegler-type catalysts polymerize ethylene at lowtemperatures and pressures to form resinous polyethylene. ByZiegler-type catalyst is meant a catalyst formed by combining anorganometallic compound in which the metal is from Groups IA, ILA, HEand IIIA of the Periodic Table in Demings General Chemistry (5th Ed),John Wiley and Sons, which is reprinted in the Handbook of Chemistry andPhysics, 31st Ed. (1949), Chemical Rubber Publishing Co., p. 336, with ahalide of a metal from Groups IVB, VB or VIB of the same Periodic Table.

Some of the metal halides used in producing a Zieglertype catalyst arethe chlorides and bromides of titanium, zirconium, vanadium, chromium,molybdenum and tungsten With the titanium and vanadium trichlorides andtribromides being preferred.

Particularly suitable organometallic compounds are the alkyl, andespecially the lower alkyl, compounds of metals of Groups IA, IIA, HEand IIIA of the Periodic Table, such as aluminum, zinc, cadmium,beryllium and lithium. Organometallic compounds in which the metal isattached to cycloalkyl radicals or aromatic radicals, as well ashalogenated compounds such as the dialkyl aluminum chlorides, are alsosuitable.

Examples of suitable organometallics useful in forming the Ziegler-typecatalyst are the dialkyl cadmiums such as diethylcadmium,dimethylcadmium and diisobutylcadmium, the dialkylzincs such asdiethylzinc and dibutylzinc, the alkylaluminums such astriethylaluminum, triisobutylaluminum, diisobutylaluminum hydride anddiethylaluminum chloride, the compounds butyllithiurn anddiethylberyllium, and the aryl metal compounds such as diphenylcadmium,dinaphthylzinc and phenyllithium.

The Ziegler-type catalyst is conveniently produced by reacting theorganometallic compound With the metallic halide in the presence of ahydrocarbon solvent such as isooctane, n-heptane or benzene. The molarratio between the organometallic compound and the halogenated metal maybe varied within wide limits. A ratio of about 0.25 to about 4 moles ofhalogenated compound, such as a titanium or vanadium trichloride, to 1mole of the organometallic compound is suitable. A typical catalystsystem could be composed of triisobutylaluminum and titanium trichloridecombined in an equimolar ratio.

ice

Polymerization of ethylene with a Ziegler-type catalyst is usuallyetlected by contacting ethylene with the catalyst in the presence of aninert solvent such as benzene or a saturated hydrocarbon like isooctane,n-hexane, pentane, decane or cyclohexane. The reaction is generallyeffected at a temperature of about 0 to 200 C., preferably at 25 to C.,and at pressures of about atmospheric or slightly above.

According to the present invention it has been discovered that effectingthe polymerization of ethylene with an additive modified Ziegler-typecatalyst results in a significant increase in the polymerization rateand/or polymer linearity as evidenced by increased density and a minimumof chain branching, as Well as control of the molecular weight of thepolyethylene. These additive modified catalysts comprise the reactionproduct of an organometallo compound and a metal halide of aconventional Ziegler-type catalyst and a chelate forming polyamine oraminoether.

By polyamine is meant a compound containing at least two nitrogen atomspresent as substituted or unsubstituted amine groups. By aminoe-ther ismeant a compound having both an amino nitrogen atom and an ether oxygenatom in the molecule. The aminoethers and polyamines which form chelateswith metals are the preferred components since they give superiorcatalysts when chemically combined with the organometallo compound andmetal halide.

Representative aminoethers that can be used include N-ethylmorpholine,Z-ethoxyethylamine, bis(2-ethoxyethyDamine, N,N-diethylaminomethylmethyl ether and N,N-diethylaminoethyl methyl ether.

Representative polyamines that can be used include N,N,N',N'-tetramethylethylenediamine N ,N,N ,N-tetramethylmethylenediamine,

1,3 -bis (dimethylamino )butane,

3- diethylamino propylamine, N,N-diethylethylenediamine,N,N,N"-trimethyl diethylenetriamine, N-phenyl-2-methyl-1,2-propanediamine,

2- (Z-N-pyrrolidinoethyl) piperidine, Z-aminopyridine,N,N,N'-trimethylethylenediamine, N,N-dibenzylethylenedia mine,

l,3-bis (dimethylamino propanol-Z,

ldimethylamino -4-aminopentane, N,N-diphenylethylenediamine,alpha,alpha-ethylenediimino-di (orthocresol) N-(Z-hydroxypropyl-2-methyll ,2-propanediamine, N,N,N,N-tetrarnethyl-1,3 -butanediarnine,N,N,N',N-tetramethyl-1,3 -propanediamine,

2- diallylamino ethylamine, N-benzyl-N,N'-dimethylethylenediamine,N,N'-dimethylethylenediamine,

3- (dirnethylamino propylamine,

N,N, "trimethyldiethylenetriamine, 2,2'-bipyridine,

N- Z-hydroxypropyl) ethylenedi amine, N,N,N',N-tetrakis-(2-hydroxypropyl) ethylenediamine, N- (Z-aminoethyl piperazine,

N-methyl piperazine,

1,4-bis Z-hydroxypropyl -2-methyl piperazine,N,N,N,N-tetramethyl-1,4-butanediamine and N,N',N-triethyldiethylenetriamine.

The catalysts useful in the process of this invention are convenientlyformed by reacting at least one of the polyamine or aminoether additiveswith a metal halide and organometallo compound of a conventionalZiegler-type catalyst system in an inert solvent. Thus, by way ofillustration, the additive can be added to titanium or vanadiumtrichloride prior to the addition of the organometallic compound, or thecatalyst components can be added to an inert solvent present with theethylene to be polymerized. Furthermore, two or more additives can beused if desired.

In general, up to about 0.75 mole of additive per mole of organometalliccompound is effective in increasing the polymerization rate and/ordensity of the polyethylene. However, about 0.05 to about 0.5 mole ofadditive for each mole of organornetallic compound is advisably used.

In the preparation of the active catalyst of this invention by combiningthe catalyst component in an inert solvent, a chemical reaction occurs,usually evidenced by a color change or formation of a black precipitate.With many of the catalyst combinations, the chemical reaction occurs atmoderately elevated temperatures, such as about 6080 C., although withsome additives higher temperatures up to about 100 C. can be used. Withother additives lower temperatures are sufficient to initiate thecatalyst forming reaction. However, other variables such asconcentration of the catalyst components in the inert solvent, time ofcontact and presence or absence of ethylene will also affect thetemperature at which the reaction occurs. This reaction, which resultsin the production of the improved catalyst, does not occur in theabsence of the additive component of this invention.

The modified catalyst is conveniently prepared by first reacting themetal halide with the additive in an inert solvent, and advisably in aninert atmosphere, adding the organo-metallic component to the resultingslurry and then allowing it to react. The ethylene can then be added tothe catalyst slurry at polymerization temperature or the catalyst slurrycan be transferred to a polymerization reactor. Alternatively, theethylene can be present during the formation of the catalyst.

The most active catalysts are those prepared from the metal halideshaving a valance of 3 or less, such as titanium trichloride and vanadiumtrichloride. The most useful catalysts for polymerizing ethylene appearto be those prepared from an alkylaluminum, an additive and a vanadiumor titanium halide and particularly the trichlorides.

In the preparation of the improved catalyst with most additives, heatingthe catalyst system to the neighborhood of 100 C. and in the absence ofethylene partially or completely deactivates the catalyst. Thus, anadditive, such as a monoamine, which requires heating under theseconditions to cause the desired reaction between the catalyst componentsgives an inactive catalyst. This effect does not necessarily preventpolymerization at such temperatures, however, since in the presence ofethylene the catalyst is apparently stabilized.

The polymerization of ethylene employing the catalyst of this inventionis readily eifected using the same solvents as discussed above for thepolymerization using the conventional Ziegler-type catalysts.

The polymerization reaction can be effected from room temperature to 105C. or higher with the process preferably being effected at 60 C. to 85C. It is important to note, however, that the additive modified catalystmay be preformed or activated at temperatures higher or lower than thoseused in the ethylene polymerization itself. Temperatures of catalystformation higher than used in the polymerization may be necessary foractivation, while catalyst formation at lower temperatures than used inthe polymerization may be needed to avoid thermal instability of thecatalyst in the absence of ethylene.

Polymerization may be effected at any convenient pressure. Atmosphericpressure or slightly higher such as 30 psig is particularly suitablealthough higher pressures can be used, but are not needed.

At completion of the polymerization reaction, the polymer slurry isfiltered to isolate the resinous polyethylene. The solid product soobtained is then freed of catalyst residues by any of several knowntechniques. One method is to stir a slurry of the polyethylene in analcohol such as methanol and then remove the insoluble resinouspolyethylene by filtration to give a friable white product.

The polymerization can be adapted readily to a continuous process underthe proper conditions.

When a dialkylaluminumhydride is used as the organometallic component ofthe catalyst it may be conveniently prepared by heating thecorresponding trialkylaluminum compound in an inert solvent such asn-decane at an elevated temperature such as about to 170 C. However, themode of preparation appears to result in no significant difference inactivity of the hydride.

The following examples illustrate the invention.

Example 1 The polymerization of ethylene was accomplished usingdiisobutylaluminum hydride solutions prepared in various ways.

Batch A was prepared by refluxing a mixture of one part by volume of 25%triisobutylaluminum in isooctane and 11.5 parts by volume of n-decanefor about 2-4 hours at 136-1 48 C.

Batch B was prepared by heating a solution of 100 ml. of 25%triisobutylaluminum in isooctane and ml. of n-decane under a stream ofnitrogen until 100 ml. of liquid had distilled off. During this time (2hours) the pot temperature gradually increased to 171 C. and the headtemperature from 100 C. to 153 C. When the pot temperature reached aboutC., a gray precipitate of aluminum began to form. During the twentyminutes of distillation after the first appearance of the precipitatethe deposit became quite heavy. The precipitate was suspended in theliquid and included in the catalyst.

Ethylene polymerization runs were made using 20 ml. of thediisobutylaluminum hydride solutions prepared as above and 0.5 g. ofTiCl (5 ml. of a 10% slurry in isooctane). In the runs in which anadditive was used, it was added as 10 ml. of a 0.1 molar solution of theadditive in isooctane, corresponding to a 0.11 molar ratio of additiveto aluminum compound; however, in some runs, as noted on Table I,one-half the amount of additive was used.

Polymerization was effected by charging the catalyst and additive, whenused, into a 350 ml. jacketed bottle on a hydrogenation shaker. Ethylenefrom a reservoir at 75 p.s.i.g. was fed into the bottle at a rate tomaintain a constant pressure of 30 p.s.i.g. The polymerization waseffected at 75 C. except for one run at 85 C. The amount of ethylene gastaken up was recorded. To determine the polymerization rate the pressuredrop in the reservoir was converted to grams of ethylene consumed andthen plotted against time. The slope of the curve was taken as thepolymerization rate in grams per hour.

The polymerization was terminated, the bottle cooled and the contentsfiltered through a cloth filter with suction. The solid, insolubleproduct obtained by filtration was stirred with several portions ofmethanol in a Waring Blendor until the solid and supernatant liquidswere colorless. The solid was then dried to give a friable whiteproduct.

The measure of molecular weight was the logarithmic viscosity number(LVN) measured in tetralin at 135 C. (See Billmeyer, Textbook of PolymerChemistry, Interscience Publishers, Inc., page 128 (1957)).

The results of the polymerization experiments are shown in Table I.

TABLE I.EFFECT OF VARIOUS ADDITIVES ON ETHYLENE POLYMERIZATION Run AlkylReaction No. Additive aluminum rate Density LVN component 126-- None A946 Insol. 109---. N,N,N,N-tetra- A 60 969 2. 04

methyl methylenediamine A 60 971 1. 94 A 47 963 2. 56 B 66 975 1. 62 B.68 975 1. A 60 968 l. 94 A 40 989 1. 78 A- 64 973 1. 84 A 55 961 2. 55xyethyb- A 66 972 l. 26 amine) 139 ldo b 62 .974 1. 45 146-2-Eth0xyetl1yl- 26 959 3. 00

amine. 148.. do 29 961 2. 99 143.--- N,N,N,N-tetra- 32 063 2. 48

methylethylenedlamine. 144" do b A 28 964 2. 54. 150 Diethylamino- A 16959 Insol.

methyl methyl ether. 15l N,N,N, -tetra- A 55 969 2.13

methyl l,3-propsnediernine.

@ Run at 85 0. rather than 75 C. b 5 ml. of additive solution used.

Examlple 2 Additional runs were made using the additives of thisinvention and untreated triisobutylaluminum in the catalyst system. Allruns utilized 5 ml. of a 10% slurry of TiCl in isooctane and 10 ml. of a25% triisobutylaluminurn isooctane solution. The additive was added in10 ml. of isooctane to give an additive to aluminum ratio of 0.11 exceptfor two runs which used half the usual amount of additive solution. TheTiCl was milled 4 hours in the presence of the additive before theaddition of the alkylaluminum compound. Runs were made at 75 C. usingthe apparatus described in Example 1. The results are reported in TableII.

TABLE II.EFFECT OF ADDITIVES ON ETHYLENE POLYMERIZATION Run AdditiveRate, Density LVN No. gJhr.

l None .935 l s. 97 0 26 .9416 l 8.70 N,N,N,N'-tetramethyl- 45 9500Insol.

methylenediamine. 43 9508 Insol. 48 9480 Insol. N,N,N' 32 .9563 3. 02

ethylenediamine. Diettilhylaminomethyl methyl 12. 7 9542 Insol.

e er. Z-ethoxyethylamine 12. 9 9489 Bis(ethoxyethyl) amine 31 954 4. 38do 8 42 959 3. 52 55 960 2. 65

I 5 ml. of additive solution used.

Example 3 The eliect of temperature on ethylene polymerization wasinvestigated with and without the presence of N,N,N,N'-tetramethylmethylenediamine as an additive. Each run employed 5 ml.of a 10% slurry of TiCl in isooctane and 10 ml. of a triisobutylaluminumisooctane solution. 10 ml. of a 0.1 molar isooctane solution of theadditive was used where applicable. The TiCl was milled 4 hours in thepresence of the additive. The

The

TABLE III Tgnoip Additive Rate, DensityN,N,N,N-tetrarnethylmgthylenediamine.

Example 4 The effect of various conditions on the heat treatment oftriisobutylaluminum to form the hydride was studied.

Preparation A was made by adding ml. of decane to a 300 ml. round bottomflask, adding 100 ml. of a 25% solution of triisobutylaluminum inisooctane and heating at 169 C. until 100 ml. of distillate wascollected.

Preparation B was made by heating a 25% solution of triisobutylaluminumin decane on an oil bath until one mole equivalent of isobutylene wasrecovered.

Preparation C was prepared as Preparation B except that heating wasstopped after 0.5 mole equivalent of isobutylene was recovered.

All runs utilized 5 ml. of a 10% slurry of TiCl in isooctane and wererun at 75 C. and 30 p.s.i. Ten ml. of 0.1 molar solutions ofN,N,N,N-tetramethylmethylenediamine, andN.N,N',N'-tetramethylpropanediamine, and 5 ml. of 0.1 molar solution ofbis-(ethoxyethyl)amine, in isooctane were used. The results are given inTable IV.

The results show no significant differences in activity of the catalystsarising from these different alkyl aluminum preparations were found. Allgave very rapid polymerization rates and products of high density. Usingdifferent amounts of hydride-modified alkyl aluminum appears to havelittle efiect on the polymerization.

As is shown in Table IV, the polymer obtained by these runs had a verylow methyl content indicating a highly linear polymer.

Example 5 Additional runs were made, some with different additives. Inthese runs 0.5 gm. of titanium trichloride was weighed into a 385 ml.reactor bottle in a dry box and covered with 10 ml. of n-heptane. Thebottle was stoppered, taken out of the dry box and filled with heptaneto bring the total volume of heptane to ml. The reactor bottle wasfastened into a heating jacket on a modified Parr shaker and 5 ml. of a0.1 molar solution of the additive added followed by 10 ml. of a 0.9molar solution of diisobutylalurninum hydride in decane. The reactor washeated and agitated and when it reached 75 C., the reactor waspressurized to 30 p.s.i.g. with ethylene. Polymerization was theneffected as in Example 1 and the product isolated as indicated there.The results obtained are reported in Table V.

TABLE IV.POLYME RIZATION OF ETHYLENE WITH HYD RIDE CATALYSTS Alkyl AlkylMethyl Run Additive aluminum aluminum Reaction Density LVN content No.component component rate, g./hr. OH groups, amount, ml. 1000 C atoms169." N,N,N,N'-tetramethylmethyl- B 1O 50 971 2. 09 0. 29 cnediamine.

d 10 75 965 2. 27 10 57 959 3. 13 2?. 10 60 969 2. 27 20 978 1. 64 81 2055 967 2. 27 57 20 82 971 2. 01 45 10 75 975 l. 20 1. 65 10 971 l. 73 7810 60 971 1. 63 20 60 978 1. 15 1. 77 161. do 20 54 971 1. 45 163N,N,N,N-tetramethyl-1,3-pro- 20 53 977 1.82 96 panediamine. do 20 60971 1. 98 66 B By infrared analysis by procedure of Willbourn, J. Poly.Sc. 34, 569 (1959).

TABLE V Run Additive Rate, LVN OIL/1,000 Density No. g./hr.

5. 6 Insol. Trace 0.939 5. 3 7. 86 Trace 0.939 5. 33 Insol. Trace 0. 947do 7. 50 Insol. Nil 0.948 Tetramethyl l, 3-butanediamin 20. 4 Insol. 0.l9 0. 954 do 26. 6 Insol. Trace 0.959 Bis (dimethylamino) propanol 48. 03. 60 0.25 0.953 do 29. 3 2. 33 0.49 0.962 N, N, N, N-tetramethyl 1, 3-32. 8 Insol. 0. 19 0. 957

propanediamine. do 50. 5 Insol Trace 0. 956 Diphenylethylenediamine- 8.00 Insol Trace 0. 955 Dimethylamino propylamine 5. 46 Insol 0. 33 0. 959do 6. 18 Insol. 0.10 0.955 N, N-diethyl ethylenediamine 6. 64 Insol 0.31 0. 959 Trimethyl ethylenediamine 22. 6 Insol 0. 43 0. 959 do 15. 7Insol. Trace 0.957 Benzyl dimethyl ethylenediamme. 6. 0 Insol. 0. 25 0.960 do 7. 3 Insol. 0.38 0.958 N, N. N, N-tetramethyl 1, 7. 6 Insol.Trace 0. 954

4-butanediamine. do 7. 3 Insol. Trace 0. 952 N, N, N, N-tetran1ethyl 24.2 Insol. 0. 96 0. 963

ethylenediamine. do 26. 5 Insol 0. 65 0. 964

Example 6 that the additives of Table VI were used. The procedureAdditional polymerization runs were made using the catalyst ingredientsand amounts of Example 5 except of that in Example 5 was followed in allother respects. The results obtained are shown in Table VI.

TABLE VI Run Additive Rate, LVN Ull /1,000 Density No. g./hr.

N, tI51;diethylaminoethyl methyl 8. 4 Insol Trace 0. 942

e er. d0 10. 4 Insol. Nil 0.9519 N,N-dibenzyl ethylenedramine- 10. l)Insol. Trace 0. 9566 8. 0 Insol. 0. 10 0.9579 61. 5 1.164 0. 84 0.9723 o62. 5 1. 160 0.30 0. 9724 N, N ,N-triethyl (liethylene- 20. 4 1. 718 0.61 0. 9711 triamine.

20. 8 Insol. 0. 48 0. 9665 9. 5 Insol. Trace 0. 9512 8. 8 Insol 0. 10 0.9501 6.8 Insol 0. 10 0.9621

6. 9 Insol 0. 28 0. 9521 9. 3 Insol Trace 0. 9559 9. 3 Insol Nil 0. 95517. 2 Insol 0. 13 0. 9641 do 7. 2 Insol 0. 09 0. 9625 N, N, N,N-tetrakis(2-hydroxy- 10. 6 Insol 0. 21 0. 9690 propyl)-ethylenediamine.o 7. 4 Insol 0.44 0.9677 N-(Z-aminoethyl)-piperazine 8. 3 Insol 0. 36 0.9629 do 8. 8 Insol 0.13 0. 9641 l, 4-Bis(2-hydroxypropyl) 2- 10. 6 Insol0. 09 0.9594

methyl-piperazine. do 8.9 111501 0.15 0.9600 64. 0 Insol. 0. 27 0. 972855.0 1. 875 0.60 0.9705 5. 6 Insol. Trace 0.939 5. 3 7. 86 Trace 0.939

usual way.

Example 7 The procedure of Example was followed using vanadiumtrichloride in place of titanium trichloride, with the additives shownin Table VII. The results are given in the said table.

prises effecting the polymerization with a catalyst comprising thereaction product of a dialkylaluminum hydride, titanium tiichloride andan aminoether.

5. The process of polymerizing ethylene whch comprises effecting thepolymerization with a catalyst compris- Run No. 652 used triisobut-ylaluminum and Runs 625 and 624 used diisobutyl aluminum hydride.

Example 8 The following experiment was to determine the efiect of thechemical reaction between the catalyst components as evidenced by theformation of a black precipitate. The catalyst was prepared by adding0.5 gram of titanium trichloride to a 385 ml. reactor bottle in a drybox and then covering the TiCl with 10 ml. of n-heptane. The bottle wasstoppered, taken out of the dry box and filled with heptane to bring thetotal volume of heptane to 185 ml. The reactor bottle was fastened intoa heating jacket on a modified Parr shaker and 5 ml. of a 0.1 molarsolution of the additive added, followed by 10 ml. of a 0.9 molarsolution of diisobutylaluminum hydride in ndecane. The catalystcomponents were agitated and heated to an elevated temperature necessaryto produce a black precipitate. In some cases, Where no additive waspresent or a monoamine was used as the additive, the black precipitatedid not form, even at temperatures approaching 100 C.

The catalyst slurry was transferred to a polymerization reactor, heatedto 75 C., and the reactor pressurized to 30 p.s.i.g. with ethylene.Polymerization was then eitected as in Example 1 and the productisolated as indicated therein. The results obtained are presented inTable VIII.

Black precipitate did not form.

Various changes and modifications of the invention can be made and, tothe extent that such variations incorporate the spirit of thisinvention, they are intended to be included within the scope of theappended claims.

What is claimed is:

1. The process of polymerizing ethylene which comprises eiiecting thepolymerization with a catalyst comprising the reaction product of atrialkylaluminum, titanium trichloride and a polyamine.

2. The process of polymerizing ethylene which comprises eiiecting thepolymerization with a catalyst comprising the reaction product of atrialkylaluminum, titaniurn trichloride and an aminoether.

3. The process of polymerizing ethylene which comprises effecting thepolymerization with a catalyst comprising the reaction product of adialkylaluminum hydride, titanium trichloride and a polyamine.

4. The process of polymerizing ethylene which coming the reactionproduct of a trialkylaluminum, vanadium trichloiide and a polyamine.

6. The process of polymerizing ethylene which comprises eflecting thepolymerization with a catalyst comprising the reaction product of atrialkylaluminum, vanadium trichloride and an aminoether.

7. The process of polymerizing ethylene which comprises etfecting thepolymerization with a catalyst comprising the reaction product of adialkylaluminum hydride, vanadium trichloride and a polyamine.

8. The process of polymerizing ethylene which comprises efrecting thepolymerization with a catalyst comprising the reaction product of adialkylaluminum hydride, vanadium trichloride and an aminoether.

9. The process of polymerizing ethylene which comprises effecting thepolymerization with a polymerization catalyst comprising the reactionproduct of a member of the group consisting of trialkylaluminum anddialkylaluminum hydride, a member of the group consisting of titaniumtrichloride and vanadium trichloride and a member of the groupconsisting of polyamines and aminoethers.

10. The process of claim 9 in which the polymerization is eiiected atabout 60 C. to about C.

11. The process of polymerizing ethylene which comprises eflecting thepolymerization with a polymerization catalyst combination comprising (a)an organometallic compound in which the metal therein is selected from amember of the group consisting of Groups IIA, IIB and IIIA of thePeriodic Table, (b) a metal halide in which the metal therein isselected from a member of the group consisting of Groups IVB, VB and VIBof the Periodic Table, and (c) a member of the group consisting ofpolyamines and aminoethers.

12. The process according to claim 11 in which 0.05 to 0.75 moles of amember of the group consisting of polyamines and aminoethers is used permole of organometallic compound.

13. The process of polymerizing ethylene which comprises efiecting thepolymerization with a catalyst combination comprising atrialkylalurninum, a titanium halide and an aminoether.

14. The process of claim 2 in which the aminoether isbis-(2-ethoxyethyl) amine.

15. The process of polymerizing ethylene which comprises effecting thepolymerization with a catalyst combination comprising atrialkylalurninum, a titanium halide and a polyamine.

16. The process of claim 15 in which the poly-amine isN,N,N',N-tetramethyl-1,3-propanediamine.

17. The process of claim 15 in which the polyamine isN,N,N',N'-tetramethylmethylenediamine.

18. The process of claim 15 in which the polyamine isN,N,N,N'-tetramethylethylenediamine.

19. The process of claim 11 in which the polyamine chelates metals.

20. The process of claim 11 in which the aminoether chelates metals.

21. The process of claim 11 in which the polymeriza- 1 1 1 2 tion isefifected from about room temperature to about FOREIGN PATENTS 105 C.

22. The process of claim 11 in which the polymeriza- 554,242 5/1957Belg1um' tion is efiec ted at about 60 C. to 85 C. 809,717 3/1959 GreatBntam- 820,773 9/1959 Great Britain. References Cited by the ExaminerUNITED STATES PATENTS 2,905,645 9/ 1959 Anderson et a1. 260-94.92,932,633 4/1960 Juveland et a1. 260-949 JOSEPH L. SCHOFER, PrimaryExaminer.

LESLIE H. GASTON, JOSEPH R. LIBERMAN,

Examiners.

11. THE PROCESS OF POLYMERIZING ETHYLENE WHICH COMPRISES EFFECTING THEPOLYMERIZATION WITH A POLYMERIZATION CATALYST COMBINATION COMPRISING (A)AN ORGANOMETALLIC COMPOUND IN WHICH THE METAL THEREIN IS SELECTED FROM AMEMBER OF THE GROUP CONSISTING OF GROUPS IIA, IIB AND IIIA OF THEPERIODIC TABLE, (B) A METAL HALIDE IN WHICH THE METAL THEREIN ISSELECTED FROM A MEMBER OF THE GROUP CONSISTING OF GROUPS IVB, VB AND VIBOF THE PERIODIC TABLE, AND (C) A MEMBER OF THE GROUP CONSISTING OFPOLYAMINES AND AMINOETHERS.